Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

Liu, Yingjun; Seco, Roger; Kim, Saewung; Guenther, Alex B.; Goldstein, Allen H.; Keutsch, Frank N.; Springston, Stephen R.; Watson, Thomas B.; Artaxo, Paulo; Souza, Rodrigo A.  F.; McKinney, Karena A.; Martin, Scot T.

doi:10.1126/sciadv.aar2547

Title: Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

Journal Article · Wed Apr 11 00:00:00 EDT 2018 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aar2547· OSTI ID:1433944

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Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS)
Univ. of California, Irvine, CA (United States). Dept. of Earth System Science
Univ. of California, Berkeley, CA (United States). Dept. of Environmental Science, Policy, and Management
Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS) and Dept. of Chemistry and Chemical Biology
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Environmental and Climate Sciences
Univ. of Sao Paulo (Brazil). Dept. of Applied Physics
Amazonas State Univ., Manaus (Brazil). Dept. of Meterology
Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS); Colby College, Waterville, ME (United States). Dept. of Chemistry
Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS) and Dept. of Earth and Planetary Sciences

Nitrogen oxides (NO_x) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO_x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO_x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning. The afternoon concentrations of reactive nitrogen oxides (NO_y), indicative of NO_x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO_y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10⁶ to 1.6 × 10⁶ cm^-3. The conclusion is that, compared to background conditions of low NO_x concentrations over the Amazon forest, pollution increased NO_x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO_x in sustaining OH concentrations.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA); National Inst. of Amazonian Research (INPA); Amazonas State Univ., Manaus (Brazil); National Council for Scientific and Technological Development (CNPq); National Science Foundation (NSF); São Paulo Research Foundation (FAPESP)

Grant/Contract Number:: SC0012704; 001030/2012-4; SC0011115; SC0011122; 1628491; 1321987; 2014/05014-0; 2017/17047-0

OSTI ID:: 1433944

Report Number(s):: BNL-203529-2018-JAAM

Journal Information:: Science Advances, Vol. 4, Issue 4; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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References (51)

Amplified Trace Gas Removal in the Troposphere Hofzumahaus, A.; Rohrer, F.; Lu, K. Science, Vol. 324, Issue 5935 https://doi.org/10.1126/science.1164566	journal	June 2009
Photooxidation of trace gases in the troposphere Plenary Lecture Ehhalt, Dieter H. Physical Chemistry Chemical Physics, Vol. 1, Issue 24 https://doi.org/10.1039/a905097c	journal	January 1999
Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia de Sá, Suzane S.; Palm, Brett B.; Campuzano-Jost, Pedro Atmospheric Chemistry and Physics, Vol. 17, Issue 11 https://doi.org/10.5194/acp-17-6611-2017	journal	January 2017
Airborne observations reveal elevational gradient in tropical forest isoprene emissions Gu, Dasa; Guenther, Alex B.; Shilling, John E. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15541	journal	May 2017
Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007 Huisman, A. J.; Hottle, J. R.; Galloway, M. M. Atmospheric Chemistry and Physics, Vol. 11, Issue 17 https://doi.org/10.5194/acp-11-8883-2011	journal	January 2011
Surface diurnal cycle and boundary layer structure over Rondônia during the rainy season Betts, Alan K. Journal of Geophysical Research, Vol. 107, Issue D20 https://doi.org/10.1029/2001JD000356	journal	January 2002
The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions Guenther, A. B.; Jiang, X.; Heald, C. L. Geoscientific Model Development, Vol. 5, Issue 6 https://doi.org/10.5194/gmd-5-1471-2012	journal	January 2012
Measurements of OH and HO ₂ concentrations during the MCMA-2006 field campaign – Part 2: Model comparison and radical budget Dusanter, S.; Vimal, D.; Stevens, P. S. Atmospheric Chemistry and Physics, Vol. 9, Issue 18 https://doi.org/10.5194/acp-9-6655-2009	journal	January 2009
HO _x budgets in a deciduous forest: Results from the PROPHET summer 1998 campaign Tan, D.; Faloona, I.; Simpas, J. B. Journal of Geophysical Research: Atmospheres, Vol. 106, Issue D20 https://doi.org/10.1029/2001JD900016	journal	October 2001
Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species Atkinson, R.; Baulch, D. L.; Cox, R. A. Atmospheric Chemistry and Physics, Vol. 6, Issue 11 https://doi.org/10.5194/acp-6-3625-2006	journal	January 2006
Insights into hydroxyl measurements and atmospheric oxidation in a California forest Mao, J.; Ren, X.; Zhang, L. Atmospheric Chemistry and Physics, Vol. 12, Issue 17 https://doi.org/10.5194/acp-12-8009-2012	journal	January 2012
Atmospheric Trends and Lifetime of CH3CCI3 and Global OH Concentrations Prinn, R. G.; Weiss, R. F.; Miller, B. R. Science, Vol. 269, Issue 5221 https://doi.org/10.1126/science.269.5221.187	journal	July 1995
Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review Atkinson, Roger; Arey, Janet Atmospheric Environment, Vol. 37 https://doi.org/10.1016/S1352-2310(03)00391-1	journal	January 2003
Normal Atmosphere: Large Radical and Formaldehyde Concentrations Predicted Levy, H. Science, Vol. 173, Issue 3992 https://doi.org/10.1126/science.173.3992.141	journal	July 1971
HOx radical regeneration in the oxidation of isoprene Peeters, J.; Nguyen, T. L.; Vereecken, L. Physical Chemistry Chemical Physics, Vol. 11, Issue 28 https://doi.org/10.1039/b908511d	journal	January 2009
Isoprene photochemistry over the Amazon rainforest Liu, Yingjun; Brito, Joel; Dorris, Matthew R. Proceedings of the National Academy of Sciences, Vol. 113, Issue 22 https://doi.org/10.1073/pnas.1524136113	journal	May 2016
Evaluation of HO _x sources and cycling using measurement-constrained model calculations in a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated ecosystem Kim, S.; Wolfe, G. M.; Mauldin, L. Atmospheric Chemistry and Physics, Vol. 13, Issue 4 https://doi.org/10.5194/acp-13-2031-2013	journal	January 2013
The tropical forest and fire emissions experiment: Emission, chemistry, and transport of biogenic volatile organic compounds in the lower atmosphere over Amazonia Karl, Thomas; Guenther, Alex; Yokelson, Robert J. Journal of Geophysical Research, Vol. 112, Issue D18 https://doi.org/10.1029/2007JD008539	journal	January 2007
Maximum efficiency in the hydroxyl-radical-based self-cleansing of the troposphere Rohrer, Franz; Lu, Keding; Hofzumahaus, Andreas Nature Geoscience, Vol. 7, Issue 8 https://doi.org/10.1038/ngeo2199	journal	July 2014
Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation Liu, Y. J.; Herdlinger-Blatt, I.; McKinney, K. A. Atmospheric Chemistry and Physics, Vol. 13, Issue 11 https://doi.org/10.5194/acp-13-5715-2013	journal	January 2013
Peroxy radical isomerization in the oxidation of isoprene Crounse, John D.; Paulot, Fabien; Kjaergaard, Henrik G. Physical Chemistry Chemical Physics, Vol. 13, Issue 30 https://doi.org/10.1039/c1cp21330j	journal	January 2011
Measurements of reactive nitrogen oxides (NO _y ) within and above a tropical forest canopy in the wet season Bakwin, Peter S.; Wofsy, Steven C.; Fan, Song-Miao Journal of Geophysical Research, Vol. 95, Issue D10 https://doi.org/10.1029/JD095iD10p16765	journal	January 1990
Kinetics and Products of the Reaction of the First-Generation Isoprene Hydroxy Hydroperoxide (ISOPOOH) with OH St. Clair, Jason M.; Rivera-Rios, Jean C.; Crounse, John D. The Journal of Physical Chemistry A, Vol. 120, Issue 9 https://doi.org/10.1021/acs.jpca.5b06532	journal	September 2015
Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest Whalley, L. K.; Edwards, P. M.; Furneaux, K. L. Atmospheric Chemistry and Physics, Vol. 11, Issue 14 https://doi.org/10.5194/acp-11-7223-2011	journal	January 2011
Introduction: Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) Martin, S. T.; Artaxo, P.; Machado, L. A. T. Atmospheric Chemistry and Physics, Vol. 16, Issue 8 https://doi.org/10.5194/acp-16-4785-2016	journal	January 2016
The Amazon basin in transition Davidson, Eric A.; de Araújo, Alessandro C.; Artaxo, Paulo Nature, Vol. 481, Issue 7381 https://doi.org/10.1038/nature10717	journal	January 2012
Missing OH source in a suburban environment near Beijing: observed and modelled OH and HO ₂ concentrations in summer 2006 Lu, K. D.; Hofzumahaus, A.; Holland, F. Atmospheric Chemistry and Physics, Vol. 13, Issue 2 https://doi.org/10.5194/acp-13-1057-2013	journal	January 2013
Rapid deposition of oxidized biogenic compounds to a temperate forest Nguyen, Tran B.; Crounse, John D.; Teng, Alex P. Proceedings of the National Academy of Sciences, Vol. 112, Issue 5 https://doi.org/10.1073/pnas.1418702112	journal	January 2015
Correlation of ozone with NO _y in photochemically aged air Trainer, M.; Parrish, D. D.; Buhr, M. P. Journal of Geophysical Research: Atmospheres, Vol. 98, Issue D2 https://doi.org/10.1029/92JD01910	journal	February 1993
The MCM v3.3.1 degradation scheme for isoprene Jenkin, M. E.; Young, J. C.; Rickard, A. R. Atmospheric Chemistry and Physics, Vol. 15, Issue 20 https://doi.org/10.5194/acp-15-11433-2015	journal	January 2015
Direct detection of OH formation in the reactions of HO ₂ with CH ₃ C(O)O ₂ and other substituted peroxy radicals Dillon, T. J.; Crowley, J. N. Atmospheric Chemistry and Physics, Vol. 8, Issue 16 https://doi.org/10.5194/acp-8-4877-2008	journal	January 2008
The role of boundary layer dynamics on the diurnal evolution of isoprene and the hydroxyl radical over tropical forests Vilà-Guerau de Arellano, Jordi; Patton, Edward G.; Karl, Thomas Journal of Geophysical Research, Vol. 116, Issue D7 https://doi.org/10.1029/2010JD014857	journal	January 2011
Assessing aboveground tropical forest biomass using Google Earth canopy images Ploton, Pierre; Pélissier, Raphaël; Proisy, Christophe Ecological Applications, Vol. 22, Issue 3 https://doi.org/10.1890/11-1606.1	journal	April 2012
Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation Rohrer, Franz; Berresheim, Harald Nature, Vol. 442, Issue 7099 https://doi.org/10.1038/nature04924	journal	July 2006
On inferring isoprene emission surface flux from atmospheric boundary layer concentration measurements Vilà-Guerau de Arellano, J.; van den Dries, K.; Pino, D. Atmospheric Chemistry and Physics, Vol. 9, Issue 11 https://doi.org/10.5194/acp-9-3629-2009	journal	January 2009
Variations of OH radical in an urban plume inferred from NO ₂ column measurements : NO2 COLUMN AND VARIATIONS OF OH RADICAL Valin, L. C.; Russell, A. R.; Cohen, R. C. Geophysical Research Letters, Vol. 40, Issue 9 https://doi.org/10.1002/grl.50267	journal	May 2013
Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation Fuchs, H.; Hofzumahaus, A.; Rohrer, F. Nature Geoscience, Vol. 6, Issue 12 https://doi.org/10.1038/ngeo1964	journal	October 2013
OH and HO2 Chemistry in the urban atmosphere of New York City Ren, X. Atmospheric Environment, Vol. 37, Issue 26 https://doi.org/10.1016/S1352-2310(03)00459-X	journal	August 2003
Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon Poschl, U.; Martin, S. T.; Sinha, B. Science, Vol. 329, Issue 5998 https://doi.org/10.1126/science.1191056	journal	September 2010
Characterisation of an inlet pre-injector laser-induced fluorescence instrument for the measurement of atmospheric hydroxyl radicals Novelli, A.; Hens, K.; Tatum Ernest, C. Atmospheric Measurement Techniques, Vol. 7, Issue 10 https://doi.org/10.5194/amt-7-3413-2014	journal	January 2014
Urban photochemistry in central Tokyo: 1. Observed and modeled OH and HO ₂ radical concentrations during the winter and summer of 2004 Kanaya, Yugo; Cao, Renqiu; Akimoto, Hajime Journal of Geophysical Research, Vol. 112, Issue D21 https://doi.org/10.1029/2007JD008670	journal	January 2007
Atmospheric oxidation capacity sustained by a tropical forest Lelieveld, J.; Butler, T. M.; Crowley, J. N. Nature, Vol. 452, Issue 7188 https://doi.org/10.1038/nature06870	journal	April 2008
The Structure of Atmospheric Turbulence Monin, A. S. Theory of Probability & Its Applications, Vol. 3, Issue 3 https://doi.org/10.1137/1103023	journal	January 1958
Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget Kuhn, U.; Andreae, M. O.; Ammann, C. Atmospheric Chemistry and Physics, Vol. 7, Issue 11 https://doi.org/10.5194/acp-7-2855-2007	journal	January 2007
Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 Southern Oxidants Study Stroud, C. A.; Roberts, J. M.; Goldan, P. D. Journal of Geophysical Research: Atmospheres, Vol. 106, Issue D8 https://doi.org/10.1029/2000JD900628	journal	April 2001
The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions Guenther, A. B.; Jiang, X.; Heald, C. L. Geoscientific Model Development Discussions, Vol. 5, Issue 2 https://doi.org/10.5194/gmdd-5-1503-2012	journal	January 2012
The structure of atmospheric turbulence Appleton, E. V. Journal of Atmospheric and Terrestrial Physics, Vol. 26, Issue 12 https://doi.org/10.1016/0021-9169(64)90142-4	journal	December 1964
Introduction: Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) Martin, S. T.; Artaxo, P.; Machado, L. A. T. Atmospheric Chemistry and Physics Discussions, Vol. 15, Issue 21 https://doi.org/10.5194/acpd-15-30175-2015	journal	January 2015
Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia S., De Sá, Suzane; Jian, Wang,; Gabriel, Isaacman-VanWertz, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/ckyt-wc41	text	January 2017
Budgets of reactive nitrogen, hydrocarbons, and ozone over the Amazon forest during the wet season Jacob, Daniel J.; Wofsy, Steven C. Journal of Geophysical Research, Vol. 95, Issue D10 https://doi.org/10.1029/jd095id10p16737	journal	January 1990
Testing Atmospheric Oxidation in an Alabama Forest Feiner, Philip A.; Brune, William H.; Miller, David O. Journal of the Atmospheric Sciences, Vol. 73, Issue 12 https://doi.org/10.1175/jas-d-16-0044.1	journal	December 2016

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Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest Shrivastava, Manish; Andreae, Meinrat O.; Artaxo, Paulo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08909-4	journal	March 2019
Low-level summertime isoprene observed at a forested mountaintop site in southern China: implications for strong regional atmospheric oxidative capacity Gong, Daocheng; Wang, Hao; Zhang, Shenyang Atmospheric Chemistry and Physics, Vol. 18, Issue 19 https://doi.org/10.5194/acp-18-14417-2018	journal	January 2018
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Title: Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

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